Adsorption of ionic and neutral pharmaceuticals and endocrine-disrupting chemicals on activated carbon fiber: batch isotherm and modeling studies.

Activated carbon fiber (ACF) has received increasing attention as an adsorbent due to its excellent surface properties. However, the adsorption mechanism of ACF for micropollutants, especially those in ionic forms, has not been sufficiently characterized to date. Therefore, the adsorption property of ACF was characterized using isotherm experiments and linear free energy relationship (LFER). For the experiments, adsorption affinities of thirty-five chemicals, i.e., pharmaceuticals and endocrine-disrupting chemicals, on ACF were estimated. Afterward, the adsorption affinities were used as dependent variables to build the LFER modeling. Finally, three isolated models for each chemical species, i.e., cations, anions, and neutrals, and a comprehensive model for the whole dataset were developed. The LFER results revealed that the models for anionic and neutral compounds have high predictabilities in R2 of 0.97 and 0.96, respectively, while that for cations has a slightly lower R2 of 0.72. In the comprehensive model including cationic, anionic, and neutral compounds, the accuracy of it is 0.81. From the developed LFER model based on the whole dataset, the adsorption mechanisms of ACF for the selected substances could be interpreted, in which the terms of hydrophobic interaction, hydrogen bonding basicity, and anionic Coulombic force of the compounds were identified as the predominant interactions with ACF.

Development of quaternized polyethylenimine-cellulose fibers for fast recovery of Au(CN)2- in alkaline wastewater: Kinetics, isotherm, and thermodynamic study.

The purpose of this study was to fabricate quaternized polyethylenimine-cellulose fibers (QPCFs) for the fast recovery of Au(I) from alkaline e-waste leachate. QPCFs were prepared by quaternizing PEI-modified cellulose fibers using a (3-chloro-2-hydroxypropyl)trimethylammonium chloride solution. The maximum Au(I) adsorption capacity of QPCFs was estimated to be 109.87 ± 3.67 mg/g at pH 9.5 using the Langmuir model. The values of k1 and k2 calculated by the pseudo-first and pseudo-second-order models were 1.79 ± 0.15 min-1 and 0.045 ± 0.003 g/mg min, respectively. Adsorption equilibrium was reached within 5 min. Thermodynamic studies revealed that the Au(I) adsorption process by the QPCFs was spontaneous (ΔG° < 0) and exothermic (ΔH° < 0). The characterization and adsorption mechanism of QPCFs were investigated by Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectrometry. Quaternary amine sites were well developed in the QPCFs. Oxidation or reduction of adsorbed Au(I) was not observed. When QPCFs were applied to the solution obtained by bioleaching of e-waste, the recovery efficiencies of Au and Cu were 61.7 ± 3.1% and 11.1 ± 2.9%, respectively, indicating that QPCFs have Au selectivity. Therefore, QPCFs are suitable for actual wastewater applications because of their high adsorption performance and fast adsorption rate.

Adsorption modeling of microcrystalline cellulose for pharmaceutical-based micropollutants.

Cellulose can be considered as a raw material for the production of filters and adsorbents for the removal of micropollutants, particularly in pharmaceutical-based products. To study its applications, it is important to estimate the adsorptive interaction of cellulose with the targeted chemicals, and develop predictive models for the expandable estimation into various types of micropollutants. Therefore, the adsorption affinity between cellulose and micropollutants was measured through isotherm experiments, and a quantitative structure-adsorption relationship model was developed using the linear free energy relationship (LFER) equation. The results indicate that microcrystalline cellulose has a remarkably high adsorption affinity with cationic micropollutants. Moreover, it has interactions with neutral and anionic micropollutants, although they have relatively lower affinities than those of cations. Through a modeling study, an LFER model - comprising of excess molar refraction, polar interaction, molecular volume, and charge-related terms - was developed, which could be used to predict the adsorption affinity values with an R2 of 0.895. To verify the robustness and predictability of the model, internal and external validation studies were performed. The results proved that the model was reasonable and acceptable, with an SE = 0.207 log unit.

Ionic liquid-assisted cellulose coating of chitosan hydrogel beads and their application as drug carriers.

The present study proposes a simple yet effective method of cellulose coating onto chitosan (CS) hydrogel beads and application thereof as drug carriers. The beads were coated with cellulose dissolved in 1-ethyl-3-methylimidazolium acetate, an ionic liquid (IL) via a one-pot one-step process. Water molecules present in the CS beads diffused outward upon contact with the cellulose-IL mixture and acted as an anti-solvent. This allowed the surface of the beads to be coated with the regenerated cellulose. The regenerated cellulose was characterized by FE-SEM, FT-IR, and XRD analyses. To test potential application of the cellulose-coated CS hydrogel beads as a drug carrier, verapamil hydrochloride (VRP), used as a model drug, was impregnated into the beads. When the VRP-impregnated beads were immersed in the simulated gastric fluid (pH 1.2), the VRP was released in an almost ideal linear pattern. This easily fabricated cellulose-coated CS beads showed the possibility for application as carriers for drug release control.

Simultaneous scavenging of persistent pharmaceuticals with different charges by activated carbon fiber from aqueous environments.

The adsorptive removal possibility of persistent pharmaceuticals with different charges by activated carbon fiber (ACF) was examined. The pharmaceuticals tested included carbamazepine (CBZ), propranolol (PRO), and diclofenac (DCF), in neutral, cationic, and anionic forms, respectively, which were frequently detected in sewage. The adsorption characteristics of ACF were identified according to the kinetics, isotherm, pH, and ionic strength experiments. The results revealed that ACF can effectively remove these pharmaceuticals, and the adsorption capacities of CBZ, PRO, and DCF by ACF were 1.27 ± 0.06, 1.07 ± 0.08, and 0.95 ± 0.08 mmol g-1, respectively. Moreover, the adsorption of ACF for CBZ was independent of pH and ionic strength, whereas that of anionic diclofenac decreased at alkaline pHs and high concentrations of NaCl. Using a syringe system packed with ACF mat, the scavenging ability of intermittently generated secondary sewage was evaluated. As a result, the residual concentration of PRO and CBZ could not be even detected after consecutive 10 runs in secondary sewage mixture solution. This indicates ACF has the powerful potential for removing pharmaceutical micropollutants in the actual aqueous solutions. FTIR and XPS analyses showed that hydrophobic and π-π interactions and hydrogen bonding contributed to the adsorption process.

Biosorption of methylene blue from aqueous solution using free and polysulfone-immobilized Corynebacterium glutamicum: batch and column studies.

The amino acid fermentation industry waste, Corynebacterium glutamicum, has been found to possess excellent biosorption capacity towards methylene blue (MB). Due to practical difficulties in solid-liquid separation and biomass regeneration, C. glutamicum was immobilized in a polysulfone matrix. The pH edge experiments revealed that neutral or alkaline pH values favored MB biosorption. Isotherm experiments indicated that C. glutamicum, when in immobilized state, exhibited slightly inferior dye uptake compared to free biomass. Also considering the two forms, immobilized biomass took a long time to attain equilibrium. An attempt to identify the diffusion limitations in immobilized beads was successful, with the Weber-Morris model clearly indicating intraparticle as the rate controlling step. Regeneration of the free biomass was not possible as it tended to become damaged under strong acidic conditions. On the other hand, immobilized biomass performed well with 99% desorption of MB from the biosorbent with the aid of 0.1 mol/l HCl. The immobilized biomass was also successfully regenerated and reused for three cycles without significant loss in sorption capacity. An up-flow packed column loaded with immobilized biomass was employed for the removal of MB. The column performed well in the biosorption of MB, exhibiting a delayed and favorable breakthrough curve with MB uptake and % removal of 124 mg/g biomass and 70.1%, respectively.

A new approach to study the decolorization of complex reactive dye bath effluent by biosorption technique.

This work focused on the development of a practical biosorbent for the decolorization of textile effluents. The fermentation waste, Corynebacterium glutamicum biomass, when decarboxylated and immobilized in polysulfone matrix performed well in decolorization of simulated reactive dye bath effluent comprised of four different reactive dyes and other auxiliary chemicals. The regeneration of polysulfone-immobilized C. glutamicum was successful with the aid of 0.01 M NaOH as the eluant, which enabled the biosorbent to maintain consistent decolorization efficiency for up to 25 cycles. An up-flow packed column loaded with polysulfone-immobilized biomass performed well in the continuous treatment of Remazol effluent. Samples collected after 14 h of column operation revealed almost zero color and TOC. The column was also able to decrease the TDS level from 55,840 to 33,480 mg/L. Column regeneration experiments revealed that the biosorbent was able to continuously treat Remazol effluent over ten cycles, with more than 90.6% decolorization efficiency.

Development of a new Cr(VI)-biosorbent from agricultural biowaste.

Among useless but abundant agricultural biowastes such as banana skin, green tea waste, oak leaf, walnut shell, peanut shell and rice husk, in this study, banana skin was screened as the most efficient biomaterial to remove toxic Cr(VI) from aqueous solution. X-ray photoelectron spectroscopy (XPS) study revealed that the mechanism of Cr(VI) biosorption by banana skin was its complete reduction into Cr(III) in both aqueous and solid phases and partial binding of the reduced-Cr(III), in the range of pH 1.5-4 tested. One gram of banana skin could reduce 249.6 (+/-4.2)mg of Cr(VI) at initial pH 1.5. Namely, Cr(VI)-reducing capacity of banana skin was four times higher than that of a common chemical Cr(VI)-reductant, FeSO(4).7H(2)O. To diminish undesirable/serious organic leaching from the biomaterial and to enhance removal efficiency of total Cr, its powder was immobilized within Ca-alginate bead. The developed Cr(VI)-biosorbent could completely reduce toxic Cr(VI) to less toxic Cr(III) and could remove almost of the reduced-Cr(III) from aqueous phase. On the basis of removal mechanisms of Cr(VI) and total Cr by the Cr(VI)-biosorbent, a kinetic model was derived and could be successfully used to predict their removal behaviors in aqueous phase. In conclusion, our Cr(VI)-biosorbent must be a potent candidate to substitute for chemical reductants as well as adsorbents for treating Cr(VI)-bearing wastewaters.

Competition of Reactive red 4, Reactive orange 16 and Basic blue 3 during biosorption of Reactive blue 4 by polysulfone-immobilized Corynebacterium glutamicum.

Competition of Reactive red 4 (RR4), Reactive orange 16 (RO16) and Basic blue 3 (BB3) during biosorption of Reactive blue 4 (RB4) by polysulfone-immobilized protonated Corynebacterium glutamicum (PIPC) was investigated in batch and column mode of operations. Through potentiometric titrations, and with the aid of proton-binding model, carboxyl, phosphonate and amine were identified as functional groups of PIPC, with apparent pK(a) values of 3.47+/-0.05, 7.08+/-0.07 and 9.90+/-0.05 mmol/g, respectively. Since reactive dyes release dye anions (ROSO(3)(-)) in solutions, the positively charged amine groups were responsible for biosorption. PIPC favored biosorption at pH 3 when RB4 was studied/used as single-solute; while the presence of RR4 and RO16 severely affected the RB4 biosorption. When present as a single-solute, PIPC recorded 184.5mg RB4/g; while PIPC exhibited 126.9, 120.9 and 169.6 mg RB4/g in the presence of RR4, RO16 and BB3, respectively. In general, the accessibility of amine group depends on the molecular size, number of sulfonate groups and reactivity of each reactive dye. Single and multicomponent Freundlich equations successfully described the biosorption isotherms. With 0.1M NaOH, it is possible to reuse PIPC for RB4 biosorption in 10 repeated cycles. Column experiments in an up-flow packed column coincided with batch results, that is PIPC showed strong preference towards highly reactive and relatively small RB4 anions; however, the presence of competing dyes hinder the RB4 column biosorption performance.

Biosorption of reactive black 5 by Corynebacterium glutamicum biomass immobilized in alginate and polysulfone matrices.

Corynebacterium glutamicum, a lysine fermentation industry waste, showed promise for the removal of Reactive black 5 (RB5). Due to practical difficulties in solid-liquid separation, the free biomass was immobilized in two polymer matrices: calcium alginate and polysulfone. Initially, the optimization of biomass loading in polymeric beads and bead dosage were examined. Of the different combinations examined, 4% (with bead dosage of 2 g per 40 ml) and 14% (with bead dosage of 1 g per 40 ml) in the case of alginate and polysulfone beads, respectively, were identified as the optimal conditions. According to the Langmuir model, at pH 1, the maximum RB5 uptakes of 352, 282 and 291 mg g(-1) were observed for free, alginate and polysulfone-immobilized biomass, respectively. According to the Weber-Morris model, intraparticle diffusion was found to be the potential rate limiting step for the immobilized beads. Regeneration experiments, with 0.01 M NaOH and Na(2)CO(3) as eluents, revealed that polysulfone beads exhibited invariable RB5 uptake capacity and very high mechanical stability even at the end of twentieth cycle, confirming the technical feasibility of the biosorption process for industrial applications.

Mechanisms of the removal of hexavalent chromium by biomaterials or biomaterial-based activated carbons.

Three papers published during recent 2 years in Journal of Hazardous Materials made a mistake in analyzing chromium species in aqueous solution, resulting in incorrect elucidation of Cr(VI) biosorption; the Cr(VI) was removed from aqueous solution systems by 'anionic adsorption'. However, it has been proved that Cr(VI) is easily reduced to Cr(III) by contact with organic materials under acidic conditions because of its high redox potential value (above +1.3 V at standard condition). Therefore, it is strongly possible that the mechanism of Cr(VI) removal by biomaterials or biomaterial-based activated carbons is not "anionic adsorption" but "adsorption-coupled reduction". Thus, for researches of Cr(VI) biosorption, researchers have to analyze not only Cr(VI) but also total Cr in aqueous solution and to check the oxidation state of chromium bound on the biomaterials or activated carbons.

Ruthenium recovery from acetic acid industrial effluent using chemically stable and high-performance polyethylenimine-coated polysulfone-Escherichia coli biomass composite fibers.

Recovery of precious metal ions from waste effluents is of high concern. In general, ruthenium (Ru) is used in the Cativa process as promoter for carbonylation catalyst and discharged into acetic acid effluent. In the present work, we have designed and developed polyethylenimine-coated polysulfone-bacterial biomass composite fiber (PEI-PSBF) to recover Ru from industrial effluent. The sorbent was manufactured by electrostatic attachment of polyethylenimine (PEI) to the surface of polysulfone-biomass composite fiber (PSBF), which was prepared through spinning of the mixture of polysulfone and Escherichia coli biomass in N,N-dimethylformamide (DMF) into water. Developed PEI-PSBF was highly stable in the acetic acid effluent. The maximum sorption capacity of the developed sorbent PEI-PSBF, coated with PEI (with M.W. of 75,000), was 121.28±13.15mg/g, which was much higher than those of ion exchange resins, TP214, Amberjet 4200, and M500. The PEI-PSBF could be successfully applied in the flow-through column system, showing 120 beds of breakthrough volume.

In vitro release of metformin from iron (III) cross-linked alginate-carboxymethyl cellulose hydrogel beads.

In the present study, sodium alginate (NaAlg)/sodium carboxymethyl cellulose (NaCMC) blend hydrogel beads were prepared in ferric chloride solution. The developed hydrogel beads exhibited pH sensitive for deliver Metformin hydrochloride (MH). Preparation conditions of the beads (ferric chloride solution) were significantly affected the encapsulation efficiency, swelling and in vitro release profiles of the beads. Swelling studies were accomplished in gastric and intestine stimuli atmosphere at 37°C. The swelling studies reveal that the beads at pH 7.4 showed higher swelling properties compare to pH 1.2. Exterior morphology of beads was analyzed by scanning electron microscope. SEM indicates the surface of the beads is spherical with smooth surface and size of beads drastically reduced with increasing crosslinker concentration. The crosslinking reaction between NaAlg and NaCMC with ferric chloride was confirmed by FTIR analysis. XRD analysis indicates that MH drug molecularly dispersed in the polymer matrix. In vitro release studies of MH loaded beads showed higher release profiles at pH 7.4 compared to pH 1.2. The polymeric matrices followed slightly deviation with Fickian diffusion and fit for experimental co-relation (r(2)) values.

The role of biomass in polyethylenimine-coated chitosan/bacterial biomass composite biosorbent fiber for removal of Ru from acetic acid waste solution.

The present study is aimed at understanding the role of bacterial biomass in functionalizing polyethylenimine (PEI)-coated bacterial biosorbent fiber (PBBF). To make PBBF, chitosan/biomass composite fiber was coated with PEI and then cross-linked by glutaraldehyde. The role of biomass in the fiber was investigated through sorption experiments and SEM, FTIR and XPS analyses with differently prepared fiber sorbents. In the case that the chitosan fiber was made without the biomass, it could not be coated with PEI. Meanwhile, the chitosan/biomass composite fiber could successfully coated with PEI and primary amine groups were significantly increased on the surface of the fiber. Therefore, the biomass should be essential to make PEI-reinforced chitosan fiber.

Recovery of high-purity metallic Pd from Pd(II)-sorbed biosorbents by incineration.

This work reports a direct way to recover metallic palladium with high purity from Pd(II)-sorbed polyethylenimine-modified Corynebacterium glutamicum biosorbent using a combined method of biosorption and incineration. This study is focused on the incineration part which affects the purity of recovered Pd. The incineration temperature and the amount of Pd loaded on the biosorbent were considered as major factors in the incineration process, and their effects were examined. The results showed that both factors significantly affected the enhancement of the recovery efficiency and purity of the recovered Pd. SEM-EDX and XRD analyses were used to confirm that Pd phase existed in the ash. As a result, the recovered Pd was changed from PdO to zero-valent Pd as the incineration temperature was increased from 600 to 900°C. Almost 100% pure metallic Pd was recovered with recovery efficiency above 99.0% under the conditions of 900°C and 136.9 mg/g.

Cationic polymer-immobilized polysulfone-based fibers as high performance sorbents for Pt(IV) recovery from acidic solutions.

This work reports a novel concept for the development of a polysulfone (PS)-based fiber as a high-performance acid-tolerant adsorbent for the recovery of platinum group metals (PGMs), particularly Pt(IV), in acidic media. Polyethylenimine (PEI)-coated PS-Escherichia coli biomass composite fiber (PEI-PSBF) was prepared by spinning biomass-PS blends in water, coating with PEI and cross-linking with glutaraldehyde. The E. coli biomass on the fiber was executed as a functional group donor for binding PEI. PS fiber (PSF), PS-biomass composite fiber (PSBF), and PEI-modified PSF (PEI-PSF) were also prepared and compared with PEI-PSBF. The results of SEM and FTIR analyses revealed the presence of PEI on the surface of PEI-PSBF. Kinetic and isotherm experiments showed the negligible sorption capacity of PSF. In contrast, adsorption equilibrium on PSBF and PEI-PSBF was attained after 40 min and 6h, respectively. The maximum Pt(IV) uptake of PEI-PSBF was 6.6 times higher than that of PSBF. Pt(IV) ions were completely recovered from loaded PEI-PSBF by 0.1M thiourea in 1M HCl solution. The PEI-PSBF was also stable in 0.1M and 1M HCl solutions. The PEI-PSBF exhibited promising properties as an adsorbent for PGMs-containing acidic wastewaters.

Utilization of PEI-modified Corynebacterium glutamicum biomass for the recovery of Pd(II) in hydrochloric solution.

A new type of biosorbent was developed for binding anionic precious metals through cross-linking waste biomass Corynebacterium glutamicum with polyethylenimine (PEI). This biomass was evaluated for the removal and recovery of palladium and compared to commercial adsorbents, such as Amberjet 4200 Cl, Lewatit Monoplus TP 214, SPC-100, and SPS-200. The kinetic experiments revealed that the sorption equilibrium was reached with 30 min for the PEI-modified biomass. The maximum uptake of the biosorbent was 176.8 mg/g, which was calculated using the Langmuir model. The Pd(II) maximum uptake exhibited the following order: Amberjet 4200 Cl>Lewatit Monoplus TP 214>PEI-modified biomass>SPC-100>SPS-200. Acidified thiourea in 1.0M HCl was used to desorb Pd(II) from all of the sorbents examined.

Preparation of PEI-coated bacterial biosorbent in water solution: optimization of manufacturing conditions using response surface methodology.

The aim of this study is to optimize preparation method of polyethyleneimine (PEI)-coated bacterial biosorbent in water as reaction media using fermentation waste biomass of Corynebacterium glutamicum as a raw material. The fermentation waste biomass of C. glutamicum and Reactive Red 4 were used as model raw bacterium and pollutant. Major factors affecting the performance of PEI-coated biosorbent were the amounts of polymer (PEI) and cross-linker glutaraldehyde (GA). These factors were optimized through response surface methodology (RSM) with two-level-two-factor (2(2)) full factorial central composite design. As a result, the optimum conditions were found to be 4.29 g of PEI and 0.15 mL of GA, with 10 g of the biomass, where the sorption capacity was enhanced 4.52-fold compared to that of the raw biomass. Therefore, this simple, cost-effective, and water-based method could be a useful modification tool for the development of a high performance biosorbent for removing anionic pollutants.

Surface modified bacterial biosorbent with poly(allylamine hydrochloride): Development using response surface methodology and use for recovery of hexachloroplatinate(IV) from aqueous solution.

In this study, poly(allylamine hydrochloride) (PAA/HCl) was cross-linked with fermentation bacterial waste (Escherichia coli) in order to introduce a large amount of amine groups as binding sites for potassium hexachloroplatinate(IV), as a model anionic pollutant. The sorption performance of PAA/HCl-modified E. coli was greatly affected by the dosages of PAA/HCl and crosslinker (epichlorohydrin, ECH), and by the pH of the modification reaction medium. These factors were optimized through the response surface methodology (RSM). A three-level factorial Box-Behnken design was performed, and a second-order polynomial model was successfully used to describe the effects of PAA/HCl, ECH and the pH on the Pt(IV) uptake (R(2) = 0.988). The optimal conditions that were obtained from the RSM were 0.49 g of PAA/HCl, 0.05 mL of ECH and pH 10.02, with 1.0 g of dried E. coli biomass. The biosorption isotherm and kinetics studies were carried out in order to evaluate the sorption potential of the PAA/HCl-modified E. coli that was prepared under the optimized conditions. The sorption performance of the developed bacterial biosorbent was 4.36 times greater than that of the raw E. coli. Desorption was carried out using 0.05 M acidified thiourea and the biosorbent was successfully regenerated and reused up to four cycles. Therefore, this simple and cost-effective method suggested here is a useful modification tool for the development of high performance biosorbents for the recovery of anionic precious metals.

Platinum recovery from ICP wastewater by a combined method of biosorption and incineration.

A high performance biosorbent, polyethylenimine (PEI)-modified biomass, was prepared by attaching PEI onto the surface of inactive Escherichia coli biomass. Wastewater containing platinum was collected from an industrial laboratory for inductively coupled plasma (ICP) and used for the recovery study. The maximum platinum uptake of PEI-modified biomass was enhanced up to 108.8 mg/g compared to 21.4 mg/g of the raw biomass. Kinetic experiments revealed that sorption equilibrium could reach within 60 min for the PEI-modified biomass. The results of FTIR and XPS analysis of Pt-unloaded and Pt-loaded PEI-modified biomass indicated that electrostatic interaction was the main binding mechanism between the platinum ions and the binding sites on the surface of the biomass. Metallic form of platinum in ash was recovered by incineration with a recovery efficiency of over 98.7%. Furthermore, XPS, TEM and XRD results confirmed that the platinum recovered were both forms of Pt(0) and Pt(2+).